Water based lubricants

ABSTRACT

WATER-SOLUBLE AMINE SALTS OF STYRENE-MALEIC ANHYDRIDE COPOLYMER RESINS AND HALF-ESTERS THEREOF ARE EMPLOYED IN AQUEOUS SOLUTIONS AS COOLANTS AND LUBRICANTS FOR METAL WORKING AND OPERATIONS. METAL WORKING LUBRICANT COMPOSITIONS ARE ALSO FORMULATED WITH COMPRISE THESE AMINE SALTS ALONG WITH EXTREME PRESSURE AGENTS SUCH AS AMINE SALTS OF FATTY ACIDS AND ORGANIC PHOSPHATE ESTERS. OTHER ADDITIVES MAY ALSO BE EMPLOYED IN THE LUBRICATING COMPOSITIONS OF THIS INVENTION.

United States Patent "ice 3,645,897 WATER BASED LUBRICANTS Howard D.Gower, Munster, Ind., and Bob G. Gower, Park Forest, and David W. Young,Homewood, Ill., assignors to Aflantic Richfield Company, New York,

No Drawing. Continuation-impart of application Ser. No. 712,965, Mar.14, 1968. This application Sept. 26, 1969, Ser. No. 861,500

Int. Cl. Cm 1/28 US. Cl. 25234.7 26 Claims ABSTRACT OF THE DISCLOSUREWater-soluble amine salts of styrene-maleic anhydride copolymer resinsand half-esters thereof are employed in aqueous solutions as coolantsand lubricants for metal working and operations. Metal working lubricantcompositions are also formulated which comprise these amine salts alongwith extreme pressure agents such as amine salts of fatty acids andorganic phosphate esters. Other additives may also be employed in thelubricating compositions of this invention.

This application is a continuation-in-part of copending application Ser.No. 712,965, filed Mar. 14, 1968, now abandoned.

This invention is concerned with novel water-based coolants andlubricants for use in metal working operations. More specifically, thisinvention is directed to aqueous solutions of water-soluble amine saltsof styrenemaleic anhydride copolymer resins and half-esters thereofwhich can be employed in aqueous solution as aqueous, metal workinglubricants. This invention is also concerned with aqueous lubricatingcompositions comprising these water-soluble amine salts ofstyrene-maleic anhydride copolymers, water, and extreme pressure (EP)agents.

Lubricants suitable for use in metal fabrication such as in cutting,threading, tapping and the like, must effectively cool and lubricateboth the tool and the worked metal. During such operations an enormousamount of heat is generated at the interface of the tool and workpiecewhich must be quickly dissipated in order to prevent damage to eitherthe tool or workpiece or both. This is accomplished by flooding theinterface with a fluid having a high capacity for heat adsorption aswell as effective lubricating properties for reducing friction betweenthe tool and workpiece. The lubricants especially formulated for thesepurposes are known in the art as cutting fluids or cutting oils. Manycutting oils, especially the earliest forms thereof, consist essentiallyof an emulsion of a mineral lubricating oil in water. While thesemineral oil based cutting fluids exhibit generally good qualities ofcooling and lubrication, they have several attendant disadvantages,including instability to bacterial attack and poor corrosion inhibition.For these reasons, cutting fluid formulations have been developed whichemploy synthetic, rather than mineral oil bases. Many improvements overthe mineral oil compositions are realized in the synthetic cuttingfluids, such as stability to bacterial decomposition and improved rustinhibition. The synthetic base lubricants heretofore developed, however,have not satisfied all the requirements necessary to provide a generally3,645,897 Patented Feb. 29, 1972 well balanced, efficient cutting fluid.For, whereas one may exhibit generally good lubricating and coolingqualities, it may have an objectionable odor, be irritating to the noseand throat of the operator or cause foaming; which obscures theoperators view of the material being worked, another may have anagreeable odor, or none at all, and be non-irritating and safe for theoperator, yet fail to produce a good finished surface on the workpiece,the finish perhaps being replete with microscopic ridges, grooves andsurface cracks.

It is an object of this invention to provide an aqueous coolant formetal working which is improved with respect to bacterially-promoted orchemically-caused odor, germforming tendency, irritation of the skin,clarity and ash content. It is a further object of this invention toprovide novel emulsifying agents for use in aqueous metal workinglubricating compositions containing synthetic lubricants.

Now in accordance with the present invention is has been found thatcooling, tapping, and other machining operations of a high degree ofefiiciency are obtained when conducted in the presence of aqueoussolutions of watersoluble amine salts of styrene-maleic anhydridecopolymers. .In addition it has been found that these watersoluble aminesalts are particularly effective as emulsifiers in aqueous lubricatingcompositions containing extreme pressure agents. The amine salts of thisinvention have been found to possess long term stability and good shelflife in aqueous lubricating compositions.

The amine salts of this invention can be formed by reacting suflicientof a suitable amine with either the styrene-maleic anhydride resin orits partial ester to react with free carboxyl groups present in theresin or its partial ester. The amount of amine reacted is sufiicient tomake the salt water-soluble and is often reacted with at least about 50%or even at least about of the total carboxyl groups of the resin. Thestyrene-maleic anhydride resin is a copolymer of aboutl to 5, preferablyabout 1 to 3 moles of styrene per mole of maleic anhydride and has amolecular weight of about 700 to 80,000, preferably about 700 to 3,000.The partial esters which can be employed are often up to about 100%half-esters of the styrene-maleic anhydride copolymer, that is thecopolymer has up to about 50% of the total number of carboxyl groupsesterified, and are preferably about 25 to 60% half-esters. Theesterifyirrg alcohols with which the copolymer is reacted to form thepartial esters include the water-soluble alcohols and capped glycolscorresponding to the general formula:

wherein R and R are aliphatic hydrocarbon radicals, preferablysaturated, of about 2 to 6 carbon atoms, and x=0 to about 10 or 12. Thetotal number of carbon atoms in R and a single R is often less thanabout 7. Uncapped glycols having molecular weights of about ZOO-20,000can also be employed, however, if uncapped glycols are used it ispreferable that the styrene-maleic anhydride polymer first bepre-esterified to reduce its functionality and thus preclude theformation of an insoluble ester. That is, the resin can be esterifiedwith an alcohol or capped glycol to form, for example, and at leastabout 50% half-ester, prior to esterifying with the uncapped glycol toform the -100% half-ester, for example. Suitable alcohols and glycolsfor use in esterifying the styrene-maleic anhydride copolymer are, forexample, n-propyl alcohol, ethyl alcohol, isopropyl alcohol, t-butylalcohol, isoamyl alcohol, capped polyethylene glycols, e.g.,polyethylene glycol monobutyl ether, and capped polypropylene glycols,etc.

Preparation of the styrene-maleic anhydride copolymer can be by knownmethods. A preferred method is by solution polymerization where themonomers are polymerized in a suitable solvent employing as apolymerization catalyst a free-radical catalyst, such as a peroxide,preferably benzoyl peroxide, dicumyl peroxide or an alkyl peroxydicarbonate, at a temperature of about 75 to 300 C. or more. Suitablesolvents include the aromatic hydrocarbon solvents, such as cumene,p-cumene, xylene, toluene, etc. Other suitable solvents are the ketones,such as methylethylketone. The preferred manner of carrying out thepolymerization is by what is known as incremental feed addition. By thismethod the monomers and catalyst are first dissolved in a portion of thesolvent in which the polymerization is to be conducted and the resultingsolution fed in increments into a reactor containing solvent heated toreaction temperature, usually the reflux temperature of the mixture.

When an aromatic solvent is employed as the solvent for thepolymerization, the formation of the copolymer causes a heterogeneoussystem, the polymer layer being the heavier layer and recoverable bymerely decanting the upper aromatic solvent layer and drying. On theother hand, when a ketone is the solvent, the formed copolymer isusually soluble in the solvent media so that recovery of the productnecessitates a solvent-stripping operation.

The water-soluble, salt-forming amines having boiling points above about200 C. can be employed in the present invention to form the amine saltsof the styrenemaleic anhydride copolymer or its partial ester. Preferredamines are tertiary amines such as, for example, tributylamine,trifurfurylamine, and hydroxyl lower alkyl amines such as, for example,diethanolamines and triethanolamines. Glycol amines or capped glycolamines of molecular weights up to about 5,000 are also suitable. Theethanolamines are preferred.

From about 10 to 70, preferably about 30 to 5 5 weight percent of theamine, about to 85, preferably about 10 to 50 weight percent water; andabout 1 to 40, preferably about 1 to 10 weight percent styrene-maleicanhydried copolymer resin or partially-esterified copolymer are presentin the composition of this invention based on the weight of these threecomponents. A preferred method of reacting the amine and the copolymeris to first dissolve the amine in the Water and then add the copolymerwhile keeping the temperature below about 140 F. to minimizeevaporation. Sufficient agitation may be employed to insure completeformation.

The aqueous compositions of this invention comprising the water-solubleamine salt of styrene-maleic anhydride copolymer resins or partialesters may be employed alone as effective lubricating compositions.Alternatively, the composition of this invention may also be employed inaqueous solutions containing minor, effective amounts of water-solubleextreme pressure lubricating agents such as water-soluble amine salts oforganic phosphate ester acids or of fatty acids of 12 to carbon atoms,for example, triethanolamine oleate, diethanolamine oleate, and similarsalts of the various water-soluble amines used to form the water-solublesalts of styrene-maleic anhydride polymers of this invention. Theseextreme pressure agents are generally effective in the composition ofthe present invention when employed in amounts of from about 2-15 weightpercent, preferably about 4-10 weight percent. Where the same amine isemployed to form the styrenemaleic anhydride salt as is used to form thesalt of the fatty acid, the fatty acid may be added directly along withthe styrene-maleic anhydride resin or patrial ester to the aqueoussolution containing an amount of the amine in excess of that needed toform the styrene-maleic anhydride salt.

The organic phosphate ester acids which may be employed as E.P. agentsin the present invention can be, for instance, primary, secondary, ortertiary esters of phosphoric acid and a hydroxyl compound which can beexemplified by the (1 -0 alkanols, phenols, including thealkylmonophenols, and monoalkyl-, monoaryland monoarylalkylethers ofpolyalkylene glycols. These phosphate compounds include thosecorresponding to the follow ing general formula:

wherein R is a hydrocarbon radical having about 1 to 30, preferably 8 to18 carbon atoms, x equals 2 to 10, preferably 2, y is 0 to 20,preferably 2 to 8, and n is 1 to 2. The R groups can be alkyl, aryl ormixed alkylaryl radicals.

These phosphate esters of this invention may be oil or water-soluble,depending to a degree on the value of y, although the size of R and xmay also be factors in determining solubility. Generally oil-solubilitytends to increase with larger values of R and x while water solubilityincreases with larger values of y, for example, above about 31:8 or 10the esters tend to be Water-soluble while below y=5 they can generallybe oil-soluble. In any event, where the esters are water-insoluble,salt-forming amine, for example, triethanol-amine, can be included inthe composition to react with and solubilize the ester. At least aboutone part by Weight of amine per part of phosphate ester can often berequired to solubilize the ester in water.

Phosphate esters useful as the extreme pressure lubricant component inthe present invention include, for example, trioctyl phosphate,oxo-tridecyl phosphate, mixtures of monoand dilauryl phosphate, laurylpolyethyleneoxy phosphate esters, nonylphenylpolyethyleneoxy phosphateesters and the like. Methods of preparation of the phosphate esterssuitable for use in the composition of the present invention appear inabundance in the prior art. US. Pat. 3,033,889 to Chiddix et al. (hereinincorporated by reference), for example, discloses the preparation ofphosphate esters of branched chain (Oxo) alcohols suitable as to thephosphate lubricant in the present invention. Similarly, the preparationof suitable alkyl, aryl and mixed aryl-alkyl polyethyleneoxy phosphateesters is described in US. Pat. Nos. 3,004,056 to Nunn et al. and3,004,057 to Nunn, both patents being herein incorporated by reference.

In addition to the amine salt of the copolymer, the BF. agent, and thewater, the composition of this invention may also contain variousadditives such as, for example, about 1 to 10 weight percent of ananti-foaming agent such as hexadecyl alcohol, or other monohydricalcohols of from about 6 to 20 carbon atoms; about 2-10 weight percent,preferably about 3-9 Weight percent, boric acid or other suitable boroncompound, such as borax, which forms boric acid on hydration, or amixture of such compounds with low molecular weight amines such asmethylethyl amine or tributyl amine and sodium nitrite which can provideprotection against rust. Water-soluble glycols, such as hexylene glycolsand polyethylene glycols of up to about 5,000 molecular weight, orcapped glycols and polyglycols, such as diethyleneglycol monoethylether, have been found to prevent film formation and tackiness on themachinery or product and improve settling of fine solids forrecirculation of fluid and may be employed in amounts up to about 30,preferably about 10 to 25, Weight percent. Small amounts ofwater-soluble silicones may be added as anti-foaming agents and sodiumnitrite may also be added as a corrosion inhibitor. It is preferred thatthe lubricant composition have a viscosity of below about poise at 25 C.

In use the lubricating composition of this invention may be diluted withwater, for instance, to a concentration of 1 part by Weight of thecutting oil composition to about 5 to 100, preferably 1 to 50, parts byweight of water.

In accordance with the present invention, lubricating compositions wereformulated as follows:

EXAMPLE I Composition (wt. percent) A B O D Styrene-maleic anhydrideha1i-ester Trlethanolamine.

Borax Hexadecyl alcohol. Diethylene glycol.

Sodium nitrite Organic phosphate ester acid 3 1 50% ethylene glycolmonobutyl ether half-ester of styrene-maleic anhydride copolymer havinga molecular Weight of about 1600 and a molar ratio of styrene to maleicanhydride of 1:1.

2 Reaction product of styrene-maleic anhydride copolymer having a moleratio of styrene to maleic anhydride of 2:1 and molecular weight ofabout 1800 and methoxy polyethylene glycol of molecular weight 350.

Mixture of approximately equal amounts of primary and secondary)phosphate esters of the oxyethylene ether of x0 tridecyl alcohol, theether containing an average of 5 oxyethylene groups.

Surface grinder tests were preformed on hard alloy cast iron using acarborundum wheel. Results are compared in Table I using Composition Dof Example I at a dilution of 1 part of cutting oil lubricant to 50parts of water and a commercial water-soluble metal cutting fluid at thesame dilution.

1 Grind ratio=metal removed/wheel wear: tests were conducted at agrinding wheel speed of 2,860 r.p.m. moving the specimen back and forthfor the indicated number of passes over the Wheel.

EXAMPLE II Other fluids were prepared according to the followingformulations:

Constituent Fluid A Fluid B Styrene-maleic anhydride copolymerhalf-ester 2 2 Hexylene glycol 15 15 Diethanolamine 50 50 Extremepressure phosphate a 5 Hexadecyl alcohol 5 5 Water 23 18 Siliconeanti-foam agent 0. 3

1 Reaction product of styrenc-maleic anhydride copolymer having a moleratio of styrene to maleic anhydride of 1:1, and molecular weight oibabout 1500 and methoxy polyethylene glycol of molecular weight of a out350.

2 Organic phosphate ester acid of Example I.

NOTE.-Fl11id5 A and B passed the skin irritation tests.

Surface grinted tests, as in Example I, Table I, and tapping tests wereperformed with composition B and commercial water-soluble metal cuttingfluids at the same dilution. The results are reported in Table II.

TABLE II Tapping torque test I Metal Steel A 9 Steel B 3 Steel C 4 Tap:60% Express Torque, percent reference Sample: 1:10 H2O dilution (in.lbs/percent reference) Composition X 321/185 446/255 444/120 CompositionY 284/171 363/204 423/110 Composition Z 415/200 413/220 392/107Composition B 336/ 170 398/226 505/115 1 Composition X was used as areference by dividing the torques for each sample by reference torquesto give percent reference.

2 A.I.S.I. No. 1117.

3 A.I.S.I. No. 8620.

4 A.I.S.I. No. 9810.

5 Compositions X, Y and Z are commercial fluids.

f Grind ratio=metal removed/wheel wear, tests were conducted at agrinding wheel speed of 2,860 r.p.m., moving the specimen back and forthfor the indicated number of passes over the wheel. The amount of metalremoved and the amount oi wheel wear were determined for each series ofpasses and the grinding ratio for each series computed therefrom. Othertest conditions follow this table.

In the grinding tests the following materials and procedures were used.

Grinding Wheel Norton mesh aluminum oxide type wheel, 8" x x 1% hole.Step dressed to provide a working width of approximately 0.275" with theremainder undercut some 0.040" to 0.060" to provide a reference surfacefor wear measurement.

Work material AISI E 52100 (modified) steel identified as PS 216 fromPeterson Steel, Inc., Melrose Park, Ill. The modification from the basicspecification was approximately a 1% increase in manganese to raise thehardenability. With this modification the work material was similar toan oil hardening tool steel. Four pieces 6 inches long by 4 /2 inchesWide and 1 inch thick were cut from a flat bar. All surfacedecarburization was removed and the flats shaped and ground to thicknessprior to heat treatment in a controlled atmosphere furnace. The testmaterials were quenched and tempered to 61 /2 to 62% R All test surfaceswere ground after heat treatment and a new surface was used for eachfluid tested.

Test specifications Machine: 6" x 18" Norton Surface Grinder, HydraulicTable Feed.

Wheel speed: 5400 to 5800 s.f.p.m.

Cross feed: Approximately 0.50 in. per traverse.

Table speed: 26 feet/min. (Machine maximum) Down feed: 0.001 and 0.002in. per pass.

Fluid application: Approximately 1% gallons per minute. directed togrinding zone (maximum to avoid excessive splashing).

Grinding fluid: Tank (capacity 5 gallons) cleaned and flushed with cleantap water. Fluid mixed with tap water (moderate hardness) inconcentration recommended by vendor for commercial preparations, and ata weight ratio of water to concentrate of 40:1 for the concentrate ofExample I. 7 /2 gallons of mix prepared in plastic container.

With each change of fluid the first 2 quarts through the pump and linewere discarded.

As can be readily determined from the results of Table I I, Composition-B of this invention performed better than Composition X and CompositionY, and about equivalent to Composition Z in the tapping torque tests.Compositions A and B also passed the Herbert Rust Test and prevented theformation of rust on the grinder and work piece under the above testconditions. The examination of the grinder was conducted two days aftercompletion of the actual grinding and revealed no new rust formation.The Herbert Rust Test is run by pouring the lubricant composition overcast iron chips and stirring every 5 minutes for 20 minutes. The testsolution is then decanted and the chips allowed to stand in the invertedbeaker for 48 hours after which the iron chips are examined for rust.Iron chips so treated with the cutting fluids of Example II exhibited norust formation. When subjected to a foam test, which consists ofdiluting 1 part of the lubricant composition with 50 parts of water,shaking vigorously for one minute and then allowing to stand,Compositions A and B of Example II both showed good foam control with Ashowing the best performance. In about three weeks, B lost somefoambreaking action while A remained almost unchanged. Composition X andComposition Y were found to have good foam control and Composition Zalmost none.

Also in the surface grind test Composition B settled 50 75% of theswarf, and in laboratory testing, Composition A settled fines moreeffectively than Composition B at 1:50 dilution. Composition X floatedall swarf and Composition Y settled all of it. No tacky residue depositswere observed when Compositions A and B were allowed to evaporate on thegrinder, while Composition Y and Composition X left a tacky residue. Ina freeze and thaw test, solidification of Compositions A and B at 13.0F. over a 24-hour period did not occur, and restoration to originalcondition was complete in only minutes at normal temperature. Thefreeze-thaw properties of Compositions A and B, therefore, areexcellent.

Compositions A and B exhibited a very faint but pleasant odor, and ratedfair for clarity. Composition Y also rated fair while Composition X andComposition Z rated excellent for clarity. Only a trace of whitesubstance appeared to settle out when Compositions A and B were dilutedat 1:50 in hard water (1000 p.p.h. Ca.) and stored for three weeks, thushard water resistance was good. Finally, Compositions A and B caused noskin irritation when tested with animals at normal workingconcentrations of 1:20 to 1:100.

It is claimed:

1. A lubricating composition comprising an aqueous solution containing alubricating amount of a water-soluble amine salt of a copolymer resinand a minor, effective amount of a water-soluble extreme pressurelubricating agent, said amine salts being those of amines having boilingpoints above about 200 C., and said copolymer resins being selected fromthe group consisting of styrene-maleic anhydride copolymers having astyrene to maleic anhydride ratio of about 1:1 to 5:1 and a molecularweight of about 700 to 80,000 and the about to 100 percent ha1festers ofsaid styrene-maleic anhydride copolymers, in which the styrene-maleicanhydride copolymers are esterified with a water-soluble member havingthe structure wherein R and R are aliphatic hydrocarbon radicals ofabout 2 to 6 carbon atoms, the total number of carbon atoms in R and asingle R is less than about 7, and x=0 to about 12.

2. The composition of claim 1 comprising said minor efiective amount ofa water-soluble extreme pressure lubricating agent and about 1 to 40weight percent of said copolymer resin, about 10 to 70 weight percent ofsaid water-soluble amine which forms the amine salt of the copolymer andabout 10 to 85 weight percent water.

3. The composition of claim 2 comprising about 1 to 10 weight percent ofsaid copolymer resin, about to 55 weight percent of said amine and about10 to 50 weight percent water.

4. The composition of claim 1 in which the amine is triethanolamine ordiethanolamine.

5. The composition of claim 3 in which the amine is triethanolamine ordiethanolamine.

6. The composition of claim 2 in which the amine is triethanolamine ordiethanolamine and the half-ester is the half-ester of a styrene-maleicanhydride copolymer having a molecular weight of about 1800 and a molarratio of styrene to maleic anhydride of about 3 to 1 and methoxypolyethylene glycol of molecular weight about 350.

7. The composition of claim 1 which contains about 2 to 10 weightpercentof theextreme pressure lubricating agent.

8. The composition of claim 6 which containsv about.

2 to 10 weight percent of the extreme pressure lubricating agent.

pressure agent is an amine salt of a fatty acid of from 12 to 20 carbonatoms.

10. The composition of claim 8 in which the extreme pressure agent is anamine salt of a fatty acid of from 12 to 20 carbon atoms.

11., The composition of claim 7 in which the extreme pressure agent is aphosphate ester acid.

12. The composition of claim 8 in which the extreme pressure agent is aphosphate ester acid.

13. The composition of claim 9 in which the amine salt istriethanolamine or diethanolamine oleate.

14. The composition of claim 10 in which the aminev salt istriethanolamine or diethanolamine oleate and the water-soluble amine istriethanolamine or diethanolamine.

15. The composition of claim 1 in which the half-ester is the 50 percentethylene glycol monobutyl ether halfester of styrene maleic anhydridecopolymer having a mol. wt. of about 1600 and a molar ratio of styreneto maleic anhydride of 1:1.

16. The composition of claim 15 in which the amine is triethanolamine ordiethanolamine.

17. The composition of claim 7 in which the amine is triethanolamine ordiethanolamine.

18. The composition of claim 1 which contains about 1 to 10 weightpercent of an alcohol of about 6 to 20 carbon atoms as an antifoamingagent, about 2 to 10 weight percent boric acid or other boron compoundwhich forms boric acid on hydration; and up to about 30 weight percentof a compound selected from the group consisting of diethylene glycolmonoethyl ether and polyethylene glycol of molecular weight up to 5000.v

19. The composition of claim 17 which contains about 1 to 10 weightpercent of an alcohol of about 6 to 20 carbon atoms as an antifoamingagent, about 2 to 10 weight percent boric acid or other boron compoundwhich forms boric acid on hydration; and up to about 30 weight percentof a compound selected from the group consisting of diethylene glycolmonoethyl ether and polyethylene glycol of molecular weight up to 5000.

20. The composition of claim 5 which contains about 1 to 10 weightpercent of an alcohol of about 6 to 20 carbon atoms as an antifoamingagent, about 2 to 10.

23. The composition of claim 18 in which the styrenemaleic anhydridecopolymer has a molecular weight of about 700 to 3000.

24. A composition comprising an aqueous solution containing alubricating amount of a water-soluble amine salt of a copolymer resin,an alcohol of about 6 to 20 carbon atoms as an antifoaming agent, boricacid or other boron compound which forms boric acid on hydration and acompound selected from the group consisting of diethylene glycolmonoethyl ether and polyethylene glycol of molecular weight up to about5000, said amine salts being those of amines having boiling points aboveabout 200 C., and said copolymer resins being selected from the groupconsisting of styrene-maleic anhydride copolymer's' having astyrene to,maleic anhydride ratio of about 9. The composition of claim 7 in whichthe extreme 9 1:1 to 5:1 and a molecular Weight of about 700 to 80,000and the about 25 to about 100 percent half-esters of-said styrene-maleicanhydride copolymers, in which the styrene-maleic anhydride copolymersare esterified with a Water-soluble member having the structure whereinR and R are aliphatic hydrocarbon radicals of about 2 to 6 carbon atoms,the total number of carbon atoms in R and a single R is less than about7, and x=0 to about 12.

25. The composition of claim 24 which contains about 1 to 10 weightpercent of the alcohol, about 2 to 10 weight percent of the boric acidor other boron compound and up to about 30 weight percent of thecompound selected from the group consisting of diethylene glycolmonoethyl ether and polyethylene glycol.

26. The composition of claim 11 in which the styrenemaleic anhydridecopolymer has a molecular weight of about 700 to 3000.

References Cited UNITED STATES PATENTS Downing et al 25249.8 Seymour26078.5 Brillhart 11776 Rossin 1l7-139.5 Niles 117139.5 Whitebeck252-493 X Pad bury et a]. 2604l Suhrie 26078.5 Lake 25249.3 X

DANIEL WYMAN, Primary Examiner 15 W. H. CANNON, Assistant Examiner US.Cl. X.R.

I UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. w gqDated Februarv 29.41972 t fi) Howard D. Gower. Bob G. Gower and David W.Young:

It is certified that error appears in the above-identified patent andthat said Letters Patent are hereby corrected as shown below:

Column 1, line 27, after "now abandoned" add ---and copendir lgapplication Ser. No; 778,80H, filed November 25, l968.--

Column 3, line 53, reads "formation" should read --formulation- Colurm5, line 60., reads "gririted" should read --grinded-- Signed and sealedthis 27th day of June 1972.

(SEAL) Attest: I

EDWARD M'.FLETCHER, JR. ROBERT GOT'I'SCHALK Attesting OfficerCommissioner of Patents FORM P0405) uscoMM-Dc eos'lo-puo U.$. GOVERNMENTPRINTING OFFICE "I! 0-36.!34

